Complexes of 2-heptadecylimidazolines



United States Patent COMPLEXES F Z-HEPTADECYLIMIDAZOLINES John N.Hogsett, Charleston, W. Van, assignor to Union Carbide Corporation, acorporation of New York No Drawing. Application March 11, 1957 SerialNo. 645,014

10 Claims. (Cl. 260-499) This invention relates to complexesofZ-heptadecylimidazolines and to a process for their preparation. Moreparticularly, this. invention relates to chelates of2-heptadecylimidazolines, as new compositions of matter and to a processfor their preparation.

I have discovered that novel chelates of2-heptadecylimidazolines areformed by reactinga metallic compound with a Z-heptadecylimidazoline. r

An embodiment of the present invention is a class of new compositions ofmatter which arechelates formed by reacting a metallic salt with aZ-heptadecylimidazoline. A specific chelate, which is illustrative ofthis embodiment of my invention is tri(Z-heptadecylimidazoline aceticacid) aluminum III sulfate (C H O N S Al which can be represented by thestructural formula:

HOOCCH:

of such chelates are: di(heptadecylimidazoline acetic acid) magnesiumsulfate, di(heptadecylimidazoline acetic acid) magnesium chloride,di(heptadecylimidazoline acetic acid) zinc chloride,di(heptadecylimidazoline acetic acid) cadmium sulfate,di(heptadecylimidazoline acetic acid) cadmium nitrate,di(heptadecylimidazoline acetic acid) mercury sulfate anddi(heptadecylimidazoline acetic acid) mercury bromide. e a Thecompositions of my invention also include the chelates formed byreacting 2-heptadecylimidazoline with the salts of the metals of groupIII of the periodic table. Illustrative of such chelates are:triheptadecylimidazoline aluminum sulfate, triheptadecylimidazolinealuminum nitrate and triheptadecylimidazoline aluminum chloride;

. My compositions also include chelates formed by reactingacid salts ofZ-heptadecylimidazoline with the salts of the metals of group III of theperiodic table. Illustrative of such chelates are:tri(heptadecylimidazoline acetic acid) aluminum sulfate,tri(heptadecylimidazoline acetic acid) aluminum nitrate andtri(heptadecylimidazoline acetic acid) aluminum chloride.

The compositions of my invention also include the chelates formed byreacting 2-heptadecylimidazoline with the salts of the metals of groupIV of the periodic table. Illustrative of such chelates isdiheptadecylimidazoline lead nitrate.

Still other compositions Within the scope of my invention are thechelates formed by reacting the acid salts of 2-heptadecylimidazolinewith the salts of the metals of TrHZ-heptadecylimidagfiige acetic acid)aluminum III sulfate,

an at zaSsAl These compositions include the chelates formed by reactingZ-heptadecylimidazoline with the salts of the metals of group I of theperiodic table. Illustrative of such chelates are:diheptodecylimidazoline silvernitrate and diheptadecylimidazoline coppersulfate.

My compositions also include chelates formed by reacting the acid saltsof Z-heptadecylimidazoline with the salts of the metals of group I ofthe periodic table. Illustrative of such chelates are:di(heptadecylimidazoline acetic acid) sodium sulfate,di(heptadecylimidazoline acetic acid) sodium hypophosphate,di(heptadecylimidazoline acetic acid) silver nitrate,di(heptadecylimidazoline acetic acid) copper sulfate.

The chelates of my invention can also be formed by reacting 2-heptadecylimidazo line withv the salts of the metals of group II of theperiodic table. Illustrative of such chelates are:diheptadecylimidazoline zinc nitrate,

diheptadecylimidazoline zinc chloride, diheptadecylimidgroup IV of theperiodic table. Illustrative of such chelates isdi(heptadecylimidazoline acetic acid) lead nitrate.

Other compositions within the scope of my invention are the chelatesformed by reacting 2-heptadecylimidazoline with the salts of the metalsof group VI of the periodic table. Illustrative of such chelates are:triheptadecylimidazoline chromium sulfate, triheptadecylimidazolinechromium nitrate and triheptadecylimidazoline chromium chloride.

Still other compositions of my invention are the chelates formed byreacting the acid salts of Z-heptadecylimidazoline with the salts of themetals of group VI of the periodic table. Illustrative of such chelatesare: tri(heptadecylimidazoline acetic acid) chromium sulfate,tri(heptadecylimidazoline acetic acid) chromium nitrate and tri-(heptadecylirnidazoline acetic acid) chromium chloride. Othercompositions within the scope of my invention are the chelates formed byreacting Z-heptadecylimidazoline with the salts of the metals of groupVII of the periodic table. Illustrative of such chelates are:diheptadecylimidazoline manganese nitrate, diheptadeclimidazolinemanganese chloride and diheptadecylimidazoline manganese sulfate. r t

The compositions of my invention also include chelates formed byreacting the acid salts of Z-heptadecylimidazoline with the salts of themetals of group VII of the periodic table. Illustrative of such chelatesare: di(heptadecylimidazoline acetic acid) manganese nitrate,di(heptadecylimidazoline acetic acid) manganese chloride anddi(heptadecylimidazoline acetic acid) manganese sulfate.

Another group of compositions within the scope of my invention are thechelates formed by reacting 2-heptadecylimidazoline with the salts ofthe metals of group VIII of the periodic table. Illustrative of suchchelates are: triheptadecylimidazoline iron sulfate,triheptadecylimidazoline iron phosphate, triheptadecylimidazoline ironnitrate, triheptadecylimidazoline cobalt sulfate anddiheptadecylimidazoline nickel nitrate.

Still another group of compositions within the scope of my inventionarethe chelates formed by reacting the acid salts of2-heptadecylimidazoline with the salts of the metals of group VIII ofthe periodic table. Illustrative of such chelates are:tri(heptadecylimidazoline acetic acid) iron sulfate,tri(heptadecylimidazoline acetic acid) iron phosphate,tri(heptadecylimidazoline acetic acid) iron nitrate,tri(heptadecylimidazoline acetic acid) cobalt sul-' fate anddi(heptadecylimidazoline acetic acid) nickel nitrate.

Other compositions within the scope of my invention are the chelatesformed by reacting Z-heptadecylimidazoline with the salts of the metalsof the lanthanum series of the periodic table. Illustrative of suchchelates is tri- (heptadecylimidazoline) cerium acid sulfate.

Still other compositions within the scope of my invention are thechelates formed by reacting the acid salts of 2-heptadecylimidazolinewith the salts of the metals of the lanthanum series of the periodictable. Illustrative of such chelates is tri(heptadecylimidazoline aceticacid) cerium acid sulfate.

The compounds of the present invention can be prepared by a processwhich comprises bringing a 2-heptadecylimidazoline into reactiveadmixture with a metal salt under conditions to produce a chelate.

The metal salts which are best suited for use in this invention arewater-soluble. For this reason, the reaction should be conducted in asolvent medium which comprises at least 80 percent water. Other solventswhich can be used together with water are methanol, ethanol, isopropanoland pyridine. The two reactants, namely the Z-heptadecylimidazoline andthe metal salt, need not be added to the solvent in any particularorder. Preferably, however, in the case of Z-heptadecylimidazoline,

the metal salt is dissolved in water and the Z-heptadecylimidazoline isdissolved in an alcohol, such as isopropanol, and the two solutions arecombined. In the case of Z-heptadecylimidazoline acetic acid, bothreactants are preferably dissolved in water.

The reaction is preferably conducted at 20 to 30 C. but can be conductedat temperatures between about C. and about 80 C.

The following examples are illustrative:

EXAMPLE I Tri(Z-heptadecylimidazoline acetic acid) aluminum III sulfate(C H O N S Al was prepared as follows:

About 35 grams of aluminum sulfate hydrate .4 calculated percentagecomposition for a 100 percent pure compound and the actual composition(by weight) found for the aluminum III chelate prepared as describedabove are compared in Table I. In Table I, R is 2-heptadecylimidazolineacetic acid.

Table 1 PERCENTAGE COMPOSITION OF 'IRI (2-HEPTAIDECYLIM- IDAZOLINEACEIIC ACID) ALUMINUM III SULFATE Calculated,

Percent Found Element Composition Percent 3R to 1 Al; Composition Thedata obtained agree satisfactorily with the theoretical structure of thealuminum III chelate containing 3 moles of Z-heptadecylimidazolineacetic acid per mole of aluminum, in accordance with the acceptedcoordinate number of 6 for Al+++.

EXAMPLE n Tri(Z-heptadecylimidazoline acetic acid) aluminum III nitrate(C H o N Al) was prepared using the same procedure as in Example I,except that 100 grams of aluminum nitrate hydrate (Al(NO -9H O) wereused in place of the 35 grams of aluminum sulfate hydrate. The driedprecipitate which was formed had a melting point of 83-85 C. Thecalculated percent pure compound and the actual composition (by weight)found for the aluminum III chelate prepared as described above arecompared in Table II. In Table II, R is 2-heptadecylimidazoline aceticacid.

Table II PERCENTAGE COMPOSITION OF TRI (Z-HEPIADECYLIM- IDAZOLINE ACETICACID)'.ALUMINUM III NITRATE Calculated,

Percent Found, Element Composition Percent 3R to 1 A1 Composition Thedata obtained agree satisfactorily with the theoretical structure of thealuminum III chelate containing 3 moles of 2-heptadecylimidazolineacetic acid per mole of aluminum, in accordance withthe acceptedcoordinate number of 6 for Al++ EXAMPLE III Table III PERCENTAGECOMPOSITION OF TRI(2-HEPTADEOYLIM- IDAZOLINE AOETIO ACID) ALUMINUM IIICHLORIDE Calculated,

Percent Found, Percent Composition Element Composition 3R to 1 The dataobtained agree satisfactorily with the theoretical structure of thealuminum III chelate containing 3 moles of Z-heptadecylimidazolineacetic acid per mole of aluminum, in accordance with the acceptedcoordinate number of 6 for Al+++.

The other chelates of this invention can be prepared in a similarmanner.

As disclosed in copending Torgeson application, Serial No. 545,107,filed November 4, 1955, the chelates of this invention are useful asfungicides. Representative chelates contemplated herein were tested forfungicidal activity by means of the slide germination test. Essentiallythis test method consisted of germinating spores in continual contact,on glass slides, with given concentrations of the chemical under test.The germination was observed after 24 hours and the amount of thechemical needed to inhibit germination of 50 percent (L.D. 50 value) ofthe spores was determined. The procedure used is more fully set forth ina paper entitled The Slide- Germination Method of Evaluating ProtectantFungicides, published in Phytopathology, July 1943, vol. XXXIII, No. 7,pp. 627-632. Two diiierent and typical fungi were used for this test.The fungi tested were Sclerotinia fructicola (Wint.) Rehm (S.f.) andAlternaria oleraceae (A.0.). The values in Table IV below represent theparts by weight of the chelate under test, in a million parts by weightof liquid, to prevent the germination of 50 percent of the spores. Theliquid used, which of itself did not inhibit germination of the spores,was Lins solution, which consists of 10 grams of dextrose, 2.46 grams ofMgSO -7H and 100 ml. of distilled water. Ten milliliters of thissolution were added to each 100 milliliters of spore.

Table IV LDrn in parts per million Compound SJ. A.o.

a Triheptadecylimidazoline iron sulfate. Diheptadecylimidazoline zincchloride....-..

The periodic table referred to in this application is the periodic tableof the elements revised in accordance with the Journal of the AmericanChemical Society, volume 76, page 2033 (1954).

This application is a continuation-in-part of my copending application,Serial No. 545,108, filed November 4, 1955, now Patent No. 2,789,115.

I claim:

1. A chelate having the structural formula MR wherein R is a memberselected from the group consisting of Z-heptadecylimidazoline and acidsalts thereof, M is both the anion and cation of an inorganic salt of ametal of group III of the periodic table and n is an integer having avalue of-one-half the coordination number of said metal.

2. A chelate having the structural formula MR,,, wherein R isZ-heptadecylimidazoline, M is both the anion and cation of an inorganicsalt of a metal of group III of the periodic table and n is an integerhaving a value of one-half the coordination number of said metal.

3. A chelate having the structural formula MR, wherein R is an acid saltof Z-heptadecylimidazoline, M is both the anion and cation of aninorganic salt of a. metal of group III of the periodic table and n isan integer having a value of one-half the coordination number of saidmetal.

4. A chelate having the structural formula MR, wherein R isZ-heptadecylimidazoline acetic acid, M is both the anion and cation ofan inorganic salt of a metal of group III of the periodic table and n isan integer having a value of one-half the coordination number of saidmetal.

5. Tri(Z-heptadecylimidazoline acetic acid) aluminum sulfate.

6. Tri(2-heptadecylimidazoline acetic acid) aluminumnitrate.

7. Tri(2-heptadecylimidazoline acetic acid) aluminum chloride.

8. Tri(Z-heptadecylimidazoline) aluminum sulfate.

9. Tri(Z-heptadecylimidazoline) aluminum nitrate.

10. Tri(Z-heptadecylimidazoline) aluminum chloride.

References Cited in the file of this patent UNITED STATES PATENTS2,155,877 Waldmann et al Apr. 25, 1939 2,540,171 Kifi Feb. 6, 19512,789,115 Hogsett Apr. 16, 1957 FOREIGN PATENTS 531,297 Germany Aug. 7,1931 OTHER REFERENCES Klingenstcin: Ber. Deut. Chem-., vol. 28, pp.1175-76 (1895).

1. A CHELATE HAVING THE STRUCTURAL FORMULA MRN, WHEREIN R IS A MEMBERSELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMIDAZOLINE AND ACIDSALTS THEREOF, M IS BOTH THE ANION AND CATION OF AN INORGANIC SALT OF AMETAL OF GROUP 111 OF THE PERIODIC TABLE AND N IS AN INTEGER HAVING AVALUE OF ONE-HALF THE COORDINATION NUMBER OF SAID METAL.